Part X – October 1968 - Papers - Ternary Compounds with the Fe2P-Type Structure

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel